Pyrazolyl, triazolyl and tetrazolyl derivatives of group iii-a elements and their compounds with metals and preparation thereof



United States Patent PYRAZOLYL, TRIAZDLYL AND TETRAZOLYL DE- RIVATIVES OF GROUP III-A ELEMENTS AND THEIR COMPOUNDS WITH METALS AND PREP- ARATION THEREOF Swiatoslaw Trofimenlro, Philadelphia, Pa., assignor to E. I. du Pont de Nernours and Company, Wilmington, DeL, a corporation of Delaware No Drawing. Filed Aug. 5, 1964, Ser. No. 387,559

20 Claims. (Cl. 260-299) This invention is concerned with a new class of organeinorganic acids, their salts and with methods for their preparation. The organo-inorganic cations of these compounds chelate strongly with divalent transition metal cations.

The compounds of the invention may be defined by (I) in which A is an element of Group I II-A of the Periodic Table, i.e., boron, aluminum, gallium, indium, or thallium, particularly boron or aluminum; -R may be hydrogen, alkyl (particularly alkyl, cycloalkyl and aralkyl of 18 carbon atoms or less), aryl (particularly aryl and alkaryl of 18 carbon atoms or less), or cyano, with R preferably being hydrogen, alkyl and aryl defined as above or cyano; X may be N or C Y may be N or CR"; R, R" and R may be hydrogen, hydroxy, mercapto,

cyano, nitro, nitroso, carboxy, alkyl (particularly alkyl,

cycloalkyl and Iaralkyl of 18 carbon atoms or less), aryl (particularly aryl and alkaryl of 18 carbon atoms or less), halogen (i.e., Cl, Br, I, -F), perhaloalkyl (with alkyl defined as above), amino (including amino substituted with one to two alkyl or aryl groups defined as above), carbacyl (including allcylcarbonyl and arylcarbonyl with alkyl and aryl defined as above), formyl, loweralkoxy, loweralkoxycarbonyl, loweralkylmercapto, hydroxyloweralkyl, aminoloweralkyl or carboxyloweralkyl; or any two of R, R" or R on adjacent carbon atoms taken together may form, with the two carbons to which they are attached, a benzo or naphtho system on the pyrazole or triazole to which they are attached; n may be zero, 1 or 2; m is equal to the net positive charge on M, i.e., 1 or 2; M is a cation, particularly hydrogen or an ammonium, alkylammonium, arylammonium (with alkyl and aryl defined as above), sulfonium or metal ion, said metal ion having a net positive valence of 1 or 2.

In the above definition all alkyl terms are to be construed as including a preference for lower alkyl, and lower alkyl is to be understood as containing 8 or fewer carbon atoms. Amino includes disnbstituted amino in which the nitrogen is a member of a 5 or 6-membered heterocyclic ring, i.e., pyrroyl and pyridyl, as well as those disubstituted amino groups described above.

The term metal is inclusive all known metals, i.e., elements of atomic numbers 3, 4, 11-13, 1932, 37-51, 5584, 87--103 and above. Preferred metals include Li, Be, Na, Mg, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Mo, Ru, IRh, Pd, Ag, Cd, Sn, Cs, Ba, Sm, Eu, Tm, Yb, W, Re, Os, Ir, Pt, Au, Hg, Pb, Po, Pr and Ra.

The definition of M above includes metal-containing cations in which the metal has a formal valence of 2 or more, but wherein this formal valence is partially satisfied by an inorganic anion so that the net valence on M is 1 or 2. Such inorganic anions, in addition to chloride illustrated in Example I, include fluoride, bromide, iodide, sulfate, nitrate, borate, carbonate, cyanide, molybdate,

3,261,844 Patented July 19, 1966 at successively higher temperatures as shown in the following three equations:

( III R N N -noo. 2H II Y X (II) (III).

R N 9 [AR.( o :lM znn Y'X 2 (IV)) H R'\ /N\ 9 R N AR. 0 O N M59 o \N ISO-220C.

I I, II n YER z Y*X A (IV) (III) K 9 [AR( O IJM +HR Y X (3) H R\ /N\ 9 R\ N AR 0 O N MB+ o \N 260290C. I I II II Y X 3 Y-X (V) (IIIH k 9 [A( O III :IMGB+HR Iv) The above stepwise process of preparation is particularly suitable when M is an alkali metal (i.e., Li, Na, K, Rb, Cs, 0r Fr), A is boron, aluminum, or gallium, and R is hydrogen. The preparation of corresponding salts in which M is a metal other than an alkali metal is carried out by metathesis as illustrated in Examples I-VI, VII'IXTV, XVI, XIX-XXIII, and XXVH-XXX.

Another process for preparing the products of this invention involves the reaction of a compound AR with a pyrazole, triazole, or tetrazole as indicated in the following equation wherein all symbols used are defined as above. The products of Formula I are prepared by subsequent methathesis. This process is illustrated in EX- The compounds of this invention as defined in Formula I include free acids (i.e., where M is hydrogen), onium salts (i.e., where M is an ammonium, substituted ammonium or sulfonium cation), alkali metal salts where M is an alkali metal, alkaline earth metal salts where M is an alkaline earth metal, and transition metal salts where M is a transition metal. In the latter group, particularly 3 preferred transition metals are those of Groups I-B, IIB, IV-A, V-B, VI-B, VII-B, and VIII of the Deming Periodic Table.

All of the compounds of Formula I possess marked stability against decomposition by water. This is in strong contrast to the related tetrahydroborates and tetraphenylborates which are readily decomposed by water, particularly in aqueous solutions of transition metal salts.

' The free acids, onium salts, and alkali metal salts of Formula I are highly ionized in aqueous solutions and are useful as sequestering agents for heavy metals and as corrosion inhibitors.

The alkaline earth metal salts and the transition metal salts of Formula I are substantially water insoluble, can be readily purified by sulblimation without decomposition, and are characterized by being soluble in organic solvents such as chloroform, methylene chloride, phenol, ethyl acetate, hexane, dioxane, and tetrahydrofuran. These organic-soluble salts are useful as antiknock agents in gasoline.

The salts most soluble in organic solvents are those in which M is a transition metal. The transition metal salts are a particularly preferred group of the compounds of Formula I since they are strongly chelated. The chelation in these compounds occurs primarily in six-membered rings of the types in which A and M are defined as above and the NN structures are the NN portions of five-membered rings derived from compounds of Formula III as indicated in Equations 1, 2, 3, and 4. These chelate rings are highly unusual in that the rings contain no carbon atom. The strong chelation accounts for the high-temperature stability of these compounds as reflected in their ability to be sublimed without decomposition. Compounds in which M is a transition metal of valence 2 contain at least two of these chelate rings. Ring structures of type (b) are most unusual in that they have a symmetrical three-dimensional cage structure in which the three auxiliary rings represented by the NN fragments are spectroscopically equivalent.

A particularly preferred group of the compounds of Formula I are those in which A is boron or aluminum and M is a transition metal. Of these compounds, the strongest chelates are those in which A is boron.

The following examples, in which parts are by weight, describe various embodiments of the invention in greater detail. It is to be understood that these embodiments do not comprise the entire invention, but rather are intended to be illustrative of a broader inventive concept for which protection by the patent laws is being sought. The invention in its broader context finds supporting disclosure throughout the entire specification, not in the examples alone.

EXAMPLE I Pyrazole (34 parts) is dissolved in 264 parts of benzene. The solution is stirred and boron trichloride is bubbled in until a viscous syrup separates. The benzene layer is removed by decantation, and the remaining syrup (containing pyrozolonium tetra-l-pyrozolylborate) is dissolved in 150 parts of water. A concentrated aqueous solution of ferric chloride is added and a deepred slurry forms. The mixture is extracted with methylene chloride. The organic layer is separated, dried over magnesium sulfate, and filtered. Hexane is added until the product precipitates. The precipitate is separated and dried to obtain 15 parts of the dimer of (tetra-I-pyrazolylborate) iron (III) dichloride in the form of blood-red needles, melting point 320 C. B NMR: Singlet at 1420 cycles downfield from methyl borate.

Anal.Calcd. for C H N BFeCl C, 35.6; H, 2.96;

4 B, 2.68; Fe, 13.8; C1, 17.5; N, 27.6; M.W., 406 (812 for dimer). Found: C, 36.2; H, 3.14; B, 2.69; Fe, 13.7; CI, 21.1; N, 25.7; M.W., 810, 855.

EXAMPLE II Part A A syrup containing pyrazolonium tetra-1-pyrazolyl borate is prepared and dissolved in water as described in Example I. The resulting aqueous solution is divided into four equal parts.

Part B One part of the solution prepared in Part A is treated with a slight chemical excess of ferrous ion in the form of an aqueous solution of ferrous ammonium sulfate. The wine-red precipitate which forms is collected by filtration and dried to obtain bis(tetra-l-pyrazolylborate)iron (II). After recrystallization from dimethyl-formamide, this product is purified by sublimation; melting point 337- 345 C.

Anal.- Calcd. for C H N B Fe: C, 46.9; H, 3.91; Fe, 9.12; N, 36.5; B, 3.52; M.W., 614. Found: C, 47.1; H, 4.04; Fe, 9.05; N, 35.9; B, 3.75; M.W., 638, 688.

Part C The procedure of Part B is repeated except for using cupric acetate in place of ferrous ammonium sulfate.

The product is bis(tetra-l-pyrozolylborate)copper (II) which is purified by sublimation.

Part D The procedure of Part B is repeated except for using Ni(OAc) in place of ferrous ammonium sulfate. The product is bis(tetra-l-pyrazolylborate)nickel (II) which is readily purified by sublimation.

Part E The procedure of Part B is repeated except for using.

Co(OAc) in place of ferrous ammonium sulfate. The product is bis(tetra-l-pyrazolylborate)cobalt (II) which is readily purified by sublimation.

EXAMPLE III Part A An aqueous solution containing the tetra-l-pyrazolylborate ion is prepared by the procedure of Part A of Example II starting with 1360 parts of pynazole.

Part B A portion (26.5%) of the solution prepared in Part A is treated with a molecular excess of aqueous Ni(OAc) A pale lilac-colored solid precipitates. It is recrystallized from dimethylformamide to obtain 43 parts of bis(tetra- 1-pyrazolylbonate)nickel (II), melting point 35 6360 C.

Anal.Calcd. for C H N B Ni: C, 46.7; H, 3.89; Ni, 9.49. Found: C, 47.2; H, 4.08; Ni, 9.48.

Part C Part D Another portion of the solution prepared in Part A (14.7%) is treated with a molecular excess of aqueous Cu(OAc) A blue solid precipitates. It is recrystallized from dimethylformamide to obtain 43 parts of bis- (tetra-l-pyrazolylborate)copper (II), melting point 270275 C.

AnaL-Calcd. for C H N B CuaC, 46.3; H, 3.86;

Cu, 10.2. Found; C, 46.6; H, 3.95; Cu, 10.3.

EXAMPLE 1V EXAMPLE V Part A To a melt of 680 parts of pyrazole is added 108 parts of KBH The melt is heated gradually so that hydrogen evolves smoothly. A'fter about 12.1 parts of hydrogen has evolved, the melt reaches a temperature of 210 C. and heating is discontinued. The cooled product is dissolved in 5000 parts of Water and the resulting solution is divided into five equal parts.

Part B To one part of the solution prepared in Part A is added a slight molecular excess of Ni(OAc) The precipitate which forms is extracted with methylene chloride. The organic solution is dried over anhydrous magnesium sulfate and evaporated to dryness. The resulting solid is recrystallized from dimethylformamide and further purified by sublimation to obtain 59 parts of bis(hydrotri-1-pyrazolylborate)nickel (II) in the form of pale lilac crystals melting at 280-282 C.

Anal.-Calcd. for C H N B Ni: C, 44.6; H, 4.13; Ni, 12.1. Found: C, 44.6; H, 3.92; Ni, 11.9.

Part C The procedure of Part B is repeated except that in place of Ni(OAc) a solution of CoCl is employed. This yields 65 parts of bis(hydrotri-l-pyrazolylborate)- cob-alt (II) in the form of yellow crystals melting at 277278 C.

Anal.Calcd. for C H N B Co: C, 44.6; H, 4.13; Co, 12.2. Found: C, 44.8; H, 4.2.1; Co 12.0.

Part D The procedure of Part B is repeated exceptthat an aqueous solution of FeSO is used. This yields 60 parts of bis(hydrotri-l-pyrazolylborate)iron (II) in the form of wine-red crystals melting with decomoposition at 265-269 C.

Anal.-Calcd. for C H N B -Fe: C, 44.9; H, 4.16; Fe, 11.6. Found: C, 45.2; H, 4.24; Fe, 11.7.

Part E The procedure of Part B is repeated except that aqueous Cu(OAc) is used. This yields blue crystals of his- (hydrotri-l-pyrazolylborate)copper (II) melting at 245-247 C.

AnaL-Calcd. for C H N B Cu: C, H, Cu, 13.0. Found: C, 44.2; H, 4.18; Cu, 13.8.

EXAMPLE VI Part A A mixture of 1360 parts of pyrazole and 360 parts of KBH is stirred and heated at 90l20 C. until about 27 parts of hydrogen evolves. The remaining melt is solidified by cooling and dissolved in 13,300 parts of water.

Part B A portion of the aqueous solution prepared in Part A is treated with a slight molecular excess of aqeuous 6 Ni(OAc) The precipitate which forms is separated and dried to obtain bis(dihydrodi-1=pyrazolylborate)- nickel (II) in the form of orange crystals which on infrared spectral analysis exhibit a multipeak pattern in the range of 44.5,u (BH).

Part C The procedure of Part B is repeated except for using aqueous CoCl in place of Ni(OAc) The product consists of purple crystals of bis(dihyd-rodi-l-pyrazolylborate)cobalt (II) melting at 163164 C. The product exhibits a multipeak pattern in the 44.5/L region on infrared analysis.

Part D The procedure of Part B is repeated except that aqueous Cu(-OAc) is used. There is obtained bis(dihydrodi- 1-pyrazolylborate)copper (II) in the form of violet crystals. On infrared analysis, these exhibit a multipeak pattern in the region of 44.5,u.

Part E The procedure of Part B is repeated except that aqueous MnSO is employed. The product is bis(dihydrodi l-pyrazolylborate) manganese (II). On infrared analysis it exhibits a multipeak pattern in the region of 44.5,u..

EXAMPLE VII filtered, and then cooled. The resulting precipitate isseparated by filtration and dried at C./20 mm. to obtain 41 parts of potassium tetra-l-pyrazolylborate monohydrate.

Anal.-Calcd. for C H N BK-H O: C, 42.9; H, 4.17; N, 33.4; K, 11.6 Found: C, 43.3; H, 4.42; N, 33.4; K, 104. a

EXAMPLE VIII A mixture of 1360 parts of pyrazole and 270 parts of KBH; is heated until a reflux temperature of 215 C. is reached and a total of about 34.3 parts of hydrogen has evolved. The resulting product is cooled and dissolved in 10,000 pants of Water. One fifth of this solution is treated With a slight molecular excess of aqueous MnSO The precipitate which forms is separated by filtration and dried to obtain 151 parts of bis(hydrotri-l-pyrazolylborate)manganese (II). It is purified by recrystallization from dimethylformam-ide and sublimation at 250 C./1 mm.

Anal.Calcd. for C H N B Mn: C, 44.9; H, 4.17; Mn, 11.4; M.W., 481. Found: C, 45.1; H, 4.33; Mn, 10.9; M.W. 496.

EXAMPLE IX Three parts of potassium tetra-l-pyrazolylborate monohydrate, prepared as in Example VII, is dissolved in 100 parts of Water. The solution is neutralized with acetic acid. About five parts of 0.1 M aqueous Li PdCl is added. The precipitate which forms is extracted with methylene'chloride. The extract is evaporated to dryness and the residue purified by sublimation at 3 10" C./1 mm. to obtain bis(tetra-l-pyrazolylborate)palladium (II) in the form of colorless crystals.

Anal.Calcd. for C I-I N B 'Pd: C, 43.4; H, 3.62. Found: C, 43.8; H, 3.81.

EXAMPLE X A mixture of 6 8 parts of pyrazole and 18 parts of KBH is heated and stirred until all the .KBH is dissolved and about 1.2 parts of hydrogen has evolved. The product is cooled and dissolved in 100 parts of Water. There is added about 330 parts of 0.5 M Ni(OAc) The solid which precipitates is extracted with methylene chloride. The extracts are dried and chromatographed rapidly on alumina. The orange band is collected, the solvent is evaporated, and the residue recrystallized from benzene to obtain 24 parts of bis(dihydrodi-l-pyrazolylborate)nickel (II) in the form of red crystals which darken at 166 C. and decompose at 180-4182 C.

Anal.-Calcd. for CmHwNgBgNiI C, H, 16.7; M.W., 352. Found: C, 41.5; H, 4.82; Ni, 16.7; M.W., 337.

EXAMPLE X-I Part A A mixture of 148 parts of 4-ch'loropyrazole and 19 parts of KBH is heated as a melt until about 2.5 parts of hydrogen has evolved. The reaction mixture, containing potassium bydrotris(4-chloro pyrazol-1-yl)borate is cooled and dissolved in 1000 parts of water. The resulting solution is divided into five equal portions.

Part B One portion of the solution prepared in -Part A is treated with a slight molecular excess of aqueous MnSO The precipitate which forms is extracted with methylene chloride. The organic layer is separated and evaporated to dryness to obtain 15.4 parts of bis[hydrotris(4-chloropyrazol-1-yl)borate]manganese (II). This product is recrystallized from dimethylformamide and then from chlorobenzene to obtain colorless crystals melting with decomposition starting at 430 C.

Part C The procedure of Part B is repeated except that aqueous ferrous ammonium sulfate is employed in place of MnSO There is obtained 9.7 parts of bis [hydrotris (4-chloropyrazol-1-yl)borate]iron (II). It is recrystallized as in Part B to yield wine-red crystals which melt with decomposition starting at 430 C.

Part D The procedure of Part B is repeated except that aqueous cobaltous chloride is employed. There is obtained 14 parts of bis[hydrotris(4-chloropyrazol-1-y1)borate] cobalt (II). It is recrystallized as in Part B to yield yellow crystals which melt with decomposition starting at 410 C.

Part E The procedure of Part B is repeated except that aqueous Ni(OAc) is employed. There is obtained 10.3 parts of bis [hydrotris(4-chloropyrazol-1-yl)borate]nickel (II). It is recrystallized as in Part B to yield lilac crystals which melt with decomposition starting at 440 C.

Part F The procedure of Part B is repeated except that aqueous cupric acetate is employed. There is obtained 7.5 parts of bis[hydrotris(4-chloropyrazol-1-yl)borate]copper. It is recrystallized as in Part B to obtain blue crystals which melt with decomposition star-ting at 320 C.

EXAMPLE XII A solution of 33 parts of K PtCl in 1500 parts of water is treated with about 3200 parts of 0.05 M aqueous potassium tetra-l-pyrazolylborate. The solution is heated to boiling, and the precipitate which forms is separated by filtration, washed first with water and then with ethanol, and then dried to yield 27 parts of bis(-tetra-lpyrazolylborate)platinum (II) in the form of essentially colorless crystals.

EXAMPLE XII I A mixture of 740 parts of 3-methylpyrazole and 122 parts of KBH is heated to drive off. hydrogen. The resulting melt contains potassium hydrotris(3(5)-methylpyrazol-l-yl) borate and potassium tetrakis(3(5)-methylpyrazo1-1yl)borate. It is cooled and dissolved in water. The resulting aqueous solution is divided into four equal parts. The parts are treated, respectively, with slight molecular excesses of aqueous solutions of ferrous ammonium sulfate, cobaltous chloride, nickelous acetate, and cupric acetate. The precipitates which form are extracted with methylene chloride. The extracts are purified by chromatography on alumina and then dried to yield, respectively, red crystals of bis[hydrotris(3(5)- methylpyrazol-l-yl)borate]iron (II) and bis[tetrakis (3(5)-met=hylpyrazol-1-yl)borate]iron (II) yellow crystals of bis [hydrotris 3 5 -methylpyrazol-1-yl borate] cobalt (II) and bis[tetrakis(3(5)-methylpyrazol-1-yl) borate]cobalt (II); lilac crystals of bis[hydrotris(3(5)- methylpyrazol-l-yl)borate]nickel (II) and bis[tetrakis (3(5)-methylpyrazol-1-yl)borate]nickel (II); and blue crystals of bis [hydrotris(3 (5 )-methylpyrazol-1-yl)borate] copper (II) and bis[tetrakis(3(5)-methylpyrazol-l-yl) borate]copper (II).

EXAMPLE XIV Part A A mixture of 480 parts of 3,5-dimethylpyrazole and 67.5 parts of KBH is heated gradually to 250 C. until about 8.3 parts of hydrogen is evolved. The melt is cooled and dissolved in 6500 parts of Water. The solution is neutralized with acetic acid using the end-point where phenolphthalein changes from red to colorless. The solid which separates is removed by filtration. The filtrate is divided into two equal parts.

Part B One half of the filtrate from Part A is treated with a silght molecular excess of aqueous nickelous acetate. The precipitate which forms is extracted with methylene chloride and recovered from the organic solution by evaporation to obtain 11 parts of bis[hydrotris(3,5-dimethylpyrazol-l-yl)borate]nickel (II) in the form of pale lilac crystals.

Part C The procedure of Part B is repeated except for using cobaltous chloride in place of nickelous acetate. There is obtained 6.4 parts of bis[hydrotris(3,S-dimethylpyrazol-1-yl)borate]cobalt (II) in the form of yellow crystals.

Anal.Calcd. for C H N B Co: C, 55.1; H, 6.74; Co, 9.01. Found: C, 55.9; H, 6.87; Co, 9.04.

EXAMPLE XV EXAMPLE XVI Part A A mixture of 520 parts of 4-isopropylpyrazole (prepared by treatment of isopropylmalonaldehyde with hydrazine) and 93 parts of KBH is heated until the melt reaches 310 C. The melt is cooled to C., poured onto ice, and dissolved by the gradual addition of 20% hydrochloric acid. The resulting solution is divided into four parts.

Part B One part of the solution prepared in Part A is treated with 2000 parts of 0.5 M ferrous ammonium sulfate. The solid which precipitates is extracted with methylene chloride.

The organic solution is dried, filtered, and- 9 evaporated to dryness to obtain 30 parts of bis [hydrotris- (4-isopropylpyrazol-1-yl)borate]iron (II) in the storm of wine-red crystals.

Part C Part D The procedure of Part B is repeated except that aqueous Ni(OAc) is employed. There is obtained 42 parts of bis[hydrotris(4 isopnopylpyrazol 1 y l)borate]nickel (II) in the form of lilac-colored crystals. They are purified by recrystallization from a mixture of ethyl acetate, ether, and hexane and further purified by sublimation.

AnaL-Calcd. for C3 H5 N12B2Ni: C, H, Ni, 7.99. Found: C, 59.4; H, 8.11; Ni, 8.05.

Part E The procedure of Part B is repeated except that aqueous cupric acetate is employed. There is obtained 24 parts of bis[hydrotris(4-isopropylpyrazol 1 yl)borate] copper (II) in the form of blue crystals.

EXAMPLE XVII A solution of 38 parts of LiAlH in 1784 parts of ether is added slowly to a solution of 340 parts of pyrazole in 1784 parts of ether under an atmosphere of nitrogen. About 8 parts of hydrogen is evolved. The resulting solution is evaporated to dryness to yield lithium tetra-1- pyrazolylaluminate in the form of a White solid.

EXAMPLE XVIII A mixture of 54 parts of KBH and 272 parts of pyr-azole is heated together at temperatures not exceeding 115 C. until about 4.5 parts of hydrogen is evolved. The melt is decanted into 433 parts of toluene with stirring. The mixture is cooled, filtered, and the solid is washed two times with 130-part portions of toluene at 80 C. The residue is air-dried to obtain 137 parts of potassium dihydrodi-l-pyrazolylborate in the form of colorless crystals melting at 171172 C. The product shows infrared absorption in the range of 22502420 cm.-

Anal.Calcd. for C H N BK: C, 38.7; H, 4.30; N, 30.1. Found: C, 39.4; H, 4.51; N, 29.9.

EXAMPLE XIX To a solution of 420 parts of potassium dihydrodi-lpyrazolylborate in 8000 parts of water is added 1070 parts of ether. The mixture is carefully neutralized with dilute hydrochloric acid. There is a vigorous evolution of hydrogen. When gas evolution subsides, about 500 parts of 0.5 M CuSO is added. At first a precipitate forms, then there is a violent gas evolution which is controlled by pouring ether on top of the mixture. Another 1500 parts of CuSO solution is added, and the mixture is extracted with ether. Extracts tare chromatographed on alumina. Impurities are first eluted with ether and then the product is eluted with methylene chloride. This latter solution is evaporated to dryness to obtain 129 parts of bis(dihydrodi-l-pyrazolylborate)copper (II) in the form of purplish-blue crystals melting at 134135 C.

Anal.-Calcd. for C H N 'B Cu: C, 40.3; H, 4.48; Cu, 17.8; N, 31.4; M.W., 357. Found: C, 40.6; H, 4.77; Cu, 17.7; N, 31.0; M.W., 367.

EXAMPLE XX An aqueous solution of potassium tetra-l-pyrazolylborate is treated with an aqueous solution of lead nitrate. The precipitate which forms is separated and dried to yield bis (tetra-l-pyrazolylborate)lead (II) in the form of colorless crystals. They are purified by sublimation.

EXAMPLE XXI An aqueous solution of potassium tetra-l-pyrazolylborate is treated with an aqueous solution of calcium chloride. The precipitate which forms is separated and dried to yield bis(tetra-l-pyrazolylborate)calcium (II) in the form of colorless crystals. They are purified by sublimation.

EXAMPLE XXII Part A A mixture of 2880 parts of 3,5-dimethylpyrazole and 361 parts of KBH is heated until about 46 parts of hydrogen has evolved. The reaction mixture is cooled and dissolved in 15,000 parts of water. The solution is extracted six times with ether to remove excess 3,5-dimethylpyrazole. The resulting solution is divided into six equal parts.

Part B One portion of the aqueous solution prepared in Part A is treated with 1500 parts of 0.5 M FeSO The solid which precipitates is extracted with methylene chloride, and the resulting organic solution is evaporated to dryness to obtain 125 parts of bis[hydrotris(3,5-dimethylpyrazole-l-yDborate]iron (II) in the form of pale green crystals. They are purified by chromatography on alumina and further purified by vacuum sublimation. The melting point is 385 C.

Anal.-Calcd. for C H N B Fe: C, 55.4; H, 6.77; Fe, 8.60. Found: C, 56.6; H, 7.19; Fe, 8.62.

Part C The procedure of Part B is repeated except that nickelous acetate is used in place of ferrous sulfate. There is obtained 70 parts of bis[hydrotris(3,5-dimethylpyrazol-1- yl)borate]nickel (II) in the form of lilac crystals. These are purified by chromatography and vacuum sublimation as in Part B, melting point 406410 C. with decomposition.

Anal.-Calcd. for C H N B Ni: C, 55.2; H, 6.74; Ni, 8.97. Found: C, 56.7; H, 6.95; Ni, 8.89.

Part D The procedure of Part B is repeated except that cobaltous chloride is used in place of ferrous sulfate. There is obtained parts of bis[hydrotris(3,5-dimethylpyrazol- 1-yl)borate]cobalt (II) in the form of yellow crystals melting at 397402 C. They are purified as in Part B.

Anal.Calcd. for C H N H Co: C, 55.2; H, 6.74; Co, 9.01. Found: C, 55.9; H, 6.87; Co, 9.04.

Parts E and F The procedure of Part B is repeated except that cupric sulfate and manganous sulfate are used in place of ferrous sulfate to give, respectively, 200 parts of bis[hydrotris(3,5-dimethylpyrazol-1-yl)borate]copper (II) as blue crystals and 78 parts of bis[hydrotris(3,5-dimethylpyrazol-1-yl)borate]manganese (II) as colorless crystals. Each product is purified as in Part B.

EXAMPLE XXIII Part A To a solution of 580 parts of 3,5-dimethylpyrazole in 3778 parts of dimethylformamide is added 108 parts of KBH The mixture is refluxed until about 13.5 parts of impure hydrogen is evolved. The hydrogen contains some by-product dimethylamine. The resulting solution containing potassium dihydrobis(3,5-dimethylpyrazol-1- yl)borate is divided into five equal portions.

1 I Part B The procedure of Part B is repeated except that ferrous sulfate is used in place of manganous sulfate. There is obtained 31 parts of bis[dihydrobis(3,5-dirnethylpyrazol- 1-yl)borate]iron (II) in the form of wine-red crystals. After two recrystallizations from cyclohexane, the melting point is 217220 C.

Anal.-Calcd. for C H N B Fe: C, 52.1; H, 6.94; Fe 12.1; M.W., 462. Found: C, 52.5; H, 7.21; Fe, 120; M.W., 451.

Part D The procedure of Part B is repeated except that cobaltous chloride is employed. The product is recrystallized from cyclohexane to yield 21 parts of bis[dihydrobis(3,5-dimethylpyrazol-1-yl)borate]cobalt (II) in the form of purple crystals melting at 225227 C.

Anal.-Calcd. for C H N B Co: C, 51.7; H, 6.88; Co, 12.6. Found: C, 52.3; H, 7.34; C0, 12.4.

Part E The procedure of Part B is repeated except that nickelous acetate is used in place of manganous sulfate. The product is purified by sublimation to obtain five parts of his [dihydrobis 3 ,5 -dimethylpyrazoll-yl) borate] nickel (II) in the form of orange crystals which melt with decomposition at about 260 C.

Anal.Calcd. for C H N B Ni: C, 51.7; H, 6.88; Ni, 12.6. Found: C, 52.3; H, 6.98; Ni, 12.2.

EXAMPLE XXIV A mixture of 176 parts of bis(dihydrodi-l-pyrazolylborate)nickel (II) and 100 parts of 4-cyanopyrazole is heated until the mixture turns dark violet in color and hydrogen is evolved. The reaction mixture is cooled, and the resulting solid is dissolved in methylene chloride and chromatographed on alumina. On evaporation, there is obtained 89 parts of bis[hydro(4-cyanopyrazol-1-yl)di- 1-pyrazolylborate]nickel (II) in the form of purple crystals. Infrared analysis shows the presence of both BH and CN bands.

EXAMPLE XXV A mixture of 70 parts of bis(dihydrodi-1-pyrazolylborate)nickel (II) and 42 parts of 1,2,4-triazole is refluxed in about 1030 parts of xylene for three days. The mixture is cooled and filtered, and the solid residue is purified by sublimation to obtain 40 parts of bis[hydrodi- 1-pyrazolyl(1,2,4-triazol-1-yl)borate]nickel (II) in the form of lilac-colored crystals. The product is recrystallized from chlorobenzene, melting point 366367 C. with decomposition.

EXAMPLE XXVI A mixture of 70 parts of bis(dihydrodi-l-pyrazolylborate)nickel (II) and 57 parts of 3,5-dimethylpyrazole is refluxed in about 1030 parts of xylene for three days. The reaction mixture is evaporated to dryness, taken up in hexane, and purified by chromatography to obtain bis- [hydro 3,5 -di1nethylpyrazoll -yl) di-pyrazolylborate] nickel (II) in the form of lilac-covered crystals, melting point about 240 C.

EXAMPLE XXVII An aqueous solution of 33 parts of the monohydrate of potassium tetra-l-pyrazolylborate is treated with a molecular excess of aqueous zinc chloride. The precipitate which forms is collected by filtration, dried and recrystallized from chlorobenzene to obtain bis(tetra-lpyrazolylborate)zinc (II) in the form of colorless crystals melting at 322323 C.

Anal.Calcd. for C H N B Zn: C, 46.2; H, 3.85; Zn, 10.5. Found: C, 46.3;H, 3.62; Zn, 10.5.

EXAMPLE XXVIII An aqueous solution of potassium hydrotri-1-pyrazolylborate is treated with a molecular excess of aqueous zinc chloride. The precipitate which forms is extracted with methylene chloride and chromatographed on alumina. The product is recrystallized from toluene to obtain bis- (hydrotri-1-pyrazolylborate)zinc (II) in the form of colorless crystals melting at 282-284 C.

Anal.Calcd. for C13H20N12B2Zl1: C, 44.0; H, 4.08; Zn, 13.3. Found: C, 44.3; H, 4.38; Zn, 13.3.

EXAMPLE XXIX A mixture of 54 parts of KBH4 and 276 parts of 1,2,4- triazole is heated until the temperature of the melt reaches 265 C. and about 7.5 parts of hydrogen is evolved. The dark mixture is cooled to solidify and dissolved in water. The resulting aqueous solution is treated with aqueous nickelous acetate. The solid which precipitates is separated and dried to obtain bis[hydrotris(1,2,4-triaZol-1-yl) borate]nickel (II) in the form of pale lilac crystals.

EXAMPLE XXX A mixture of 54 parts of KBH; and 276 parts of 1,2,3- triazole is heated until about 6.3 parts of hydrogen has evolved. The product is dissolved in water and treated with a slight molecular excess of aqueous nickelous acetate. The precipitate which forms is separated to obtain bis[hydrotris(1,2,3-triazol-1-yl)borate1nickel (II). The infrared analysis of this product shows singlet bands for BH. By the above procedure, the corresponding compounds of iron (II), cobalt (II), and copper (II) are prepared.

, EXAMPLE XXXI Part A A mixture of 54 parts of KBH, and 340 parts of pyrazole is stirred and heated until about 8.1 parts of hydrogen is evolved. The resulting melt is cooled and poured into 1300 parts of toluene. The mixture is stirred and filtered, and the residue is washed successively with hot toluene, benzene, and ether. There remains 310 parts of potassium tetra-l-pyrazolylborate in the form of colorless crystals.

Anal.Calcd. for C H N BK: C, 45.3; H, 3.78; N, 35.2. Found: C, 43.0; H, 4.37; N, 34.0.

Part B An aqueous solution of potassium tetra-l-pyrazolylborate is treated with a molecular equivalent amount of aqueous Ni(OAc) The precipitate which forms is separated and purified by vacuum sublimation to obtain bis- (tetra-l-pyrazolylborate)nickel (II) in the form of lilaccolored crystals melting at 370372 C.

Anal.Calcd. for C H N B Ni: C, 46.7; H, 3.89; N, 36.3 Found: C, 47.0; H, 4.22; N, 37.4.

EXAMPLE XXXII A mixture of parts of phenylborondichloride in benzene is poured into a benzene solution of a molecular excess of pyrazole. The mixture warms spontaneously and a white solid separates. The mixture is extracted with water and the aqueous extracts are heated with a molecular excess of aqueous Co(OAc) The resulting slurry isextracted with methylene chloride. The organic layer is evaporated to dryness and the residue recrystallized from chlorobenzene to obtain 16 parts of bis(phenyltri-lpyrazolylborate)cobalt (II). After purification by sublimation at 300 C./1 mm., the product melts partially at 13 about 355 C. and remains darkened but still unmelted at Anal.-Calcd. for C H N B Co: C, 56.6; H, 4.40; N, 26.4. Found: C, 55.6; H, 4.36; N, 27.4.

ene chloride and adding a large excess of diethyl ether. The solid which separates is collected by filtration and dried to obtain hydrogen tetra-l-pyrazolylborate melting at 7071 C.

EXAMPLE XXYHI AnaL-Calcd. fOI C12H13N8BI C, 51.4; H, 4.64; N, 40.0.

A f 1f dd d 1 1 Found: C, 52.1; H, 4.69; N, 40.4.

queous erric su ate is a e to an aqueous so ution of potassium hydrotri-l-pyrazolylborate. The red precipi- EXAMPLE XXXVII tate which forms is extracted With methylene chloride. An aqueous solution of potassium dihydrodi-l-pyrazo- The organic layer is separated and evaporated to dryness 1O lylborate is acidified by adding an aqueous solution of an to obtain hydrotri-l-pyrazolylbonate iron (III) sulfate in equivalent amount of acetic acid. The precipitate which the form of a red solid. forms is separated and dried to obtain hydrogen dihydrodi- EXAMPLE XXXIV l-pyrazolylborate in the form of colorless crystals.

A mixture of 54 parts of KBH, and 480 parts of 3,5- EXAMPLE XXXVIH dimethylpyrazole is heated with stirring at temperatures An aqueous solution of potassium hydrotri-l-pyrazolylup to 238 C. until 6.75 parts of hydrogen is evolved. borate is acidified with a molecular equivalent amount of The melt is cooled to 200 C. and poured into 1732 parts aqueous acetic acid. The precipitate which forms is of toluene With stirring. The resulting mixture is cooled separated by filtration and dried to obtain hydrogen hyand filtered, and the residue is air-dried to obtain 114 parts droti-1-pyrazolyl borate in the form of colorless crystals. of potassium hydrotris(3,5-dimethylpyrazol-l-yl)borate in An alternative method for preparing the salts of this the form of colorless crystals wh ch melt at about 300 C. invention is by neutralizing the free acid products with and can be purified by sublimation at 290 C./ 1 mm. an appropriate base, i.e., an oxide or hydroxide. For ex- Anal.-Calcd. for C H N BK: C, 53.6; H, 6.55. ample, oniurn salts other than those described above may Found: C, 53.7; H, 6.72. be prepared by neutralizing an aqueous solution of a free EXAMPLE XXXV acid such as hydrogen tetra-l-pyrazolylborate of Example XXXVI with ammonium hydroxide, tetraethylamhhxhlre of 54 Parts of 'H4 and 2/0 Parts of 1,2,4- moni um hydroxide, methyltriphenylammonium hydroxide, thazole 1S heated thgether uhhl P of hydrogen or triet-hylsulfom' um hydroxide. The respective products evolves- The melt f and dlssolved 111 8,000 Parts which precipitate are ammonium tetra-l-pyrazolylborate, of Water- The h h 1S Wanhedhhd 1,000 Parts 9h tetraethylammonium tetra-l-pyrazolylborate, methyltri- M 2 water 15 h The preclphate phenylammonium tetra-l-pyrazolylborate and triethylsulwhich forms is collected by filtration and recrystallized fonium tetra l pyrazolylborate Similarly by employing from hot Water to obtain 39 parts of bis[hydrotris(l,2,4- the free acids of Examples XXXVH and XXXVHI the maZO1' 1y1)boratekobah (H) m the form of crys corresponding onium dihydrodi-l-pyrazolylborates and tals which do not melt at temperatures up to 390 C. onium hydr0ti l pyrazolylborates are Obtained AMI-Cami for CHHMNIBBZCO: 29-33 2-85; N, When the substituted pyrazoles shown in column A of 51.3. Found. C, 29.5, H, 2.93, N, 51.4. Table I are used in place of 3,5-dimethylpyrazole in Parts EXAMPLE XXXVI and C of Example XXIII, the iron chelate salt shown in column B is obtained. When the same substituted pyr- A solution of 180 parts of potassium tetra-l-pyrazoly lazoles are used in place of 3,5-dimethylpyrazole in Parts borate in 3,000 parts of Water is treated with 31 parts of A and E of Example XXII, the cobalt chelate salts in acetic acid The precipitate which forms is collected by column C are obtained. When the same substituted pyr filtration, washed With water and ethanol, and air-dried to 'azoles are used in place of pyrazole in Parts A and B of obtain 115 parts of colorless crystals. This product is Example XXXI, the nickel chelate salts shown in column purified by dissolving it in a minimum amount of methyl- D are obtained.

TABLE I Item A. Substituted Pyrazole B. Product from Procedure of 0. Product from Procedure of D. Product from Procedure of Example XXIII, Parts A and C Example XXII, Parts A and E Example XXXI, Parts A and B 1 3,4,5-trimethylpyrazole. Bis[dihydrobis(3,4,5-trimethylpyi'- Bis[hydrotris(3,4,5-trimethylpyr- Bis[tetrakis(3,4,5-trimetliy1pyraz01-1-y1) borate] iron (II) azo1-1-yl)borate]cobalt(II) azol-l-yl) borate]niclrel(II) 2 3-ethy1pyrazole Bis[dihydrois(3-ethylpyrazol-1- Bis[hydrotris(3-ethylpyrazol-l- Bis[tetrakis(3-ethylpyrazol-1- y1)borate1iron (II) yl)borate]cob alt (II). yl)borateln iekel(II). 3 B-ethynylpyrazole Bis[dihydrobis(3-etl1ynylpyrazol-1- Bis[hydrotris(3-ethynylpyrazol-l- Bis[tetrakis(3-ethynylpyrazol-1- yl) borate1iron (II) yl) boratelcobaltfll). yl) boratelnickel (II) 4 S-butadienylpyrazole Bis[dihydrobis(3-butadienylpyr- Bis[hydrotris(3-butadienylpyrozol- Bis[tetrakis(3-butadieny1pyrazol-1- azol-l-yl)borate]iron (II) 1-yl)b0rate]cob alt (II) yl) borate] nickel (II) 5 3-methyl-5-plienylpyr- Bis[dihydrobis(3-methy1-5-phenyl- Bis[hydrotris(3-methyl-5-phenyl- Bis[tetrakis(3-methyL5phenylazole. pyrazol-l-yl)borate]iron (II). pyrazol-1-yl)borate] cob alt (II) pyrazol-l-yl)borate]nieke1(II). 6 3,4,5-triphenylpyrazole- Bis[dihydrobis(3,4,5-triplienylpyr- Bis[hydrotris(3,4,5-triphenylpyr- Bis[tetrakis(3,4,5-triphenylpyrazol-1-yl)borate]iron (II) azol-1-yl)borate]c0b alt (II) az0l-1yl) borate]nickel (II) 7 5-chloro-3-methylpyrazole Bis[dihydrobis(5-chl0ro-3-methyl- Bis[hydrotris(5-chloro-3-methyl- Bis[tetrakis(5-chloro3-methylpyraz ol-l-yl) borate1iron (II) pyrazol-I-yl)borate1cobalt (II) pyrazol-l-yl)borate]niekel (II) 8 3-bromo-4-phenylpyrazole- Bis[dihydrobis(3 bromo-4-phenyl- Bislhydi-otris(3-bromo-4-phenyl- Bisltetrakis(3-bromo-4-phenylpyrazo1-1-yl)borate]iron (II). pyrazold-ybboratelcob alt (II) pyrazol-1-y1)b0i-ate]riickel(II) 9 4-iodopyrazo1e Bis[dihydrobis(Modopyrazol-l- Bislhydrotris(4-i0d0pyrazol-1- Bis[tetrakis(4-iodopyrazo1-1- yl)borate]irori (II) yl)borate]cobalt (II) yl)borate]nicke1(II) 10 3,5-dimethyl-4-nitroso- Bis[dihydrobis(3,5-dimethyl-4-nitro- Bis[hydrotris(3,5-dimetliyl-4-nitro- Bis[tetrakis(3,5-dimethy14-nitroyrazole. sopyrazol-l-yDborate]iron(II). sopyrazol-1-y1)borate]cob alt (II) sopyrazol-l-yl)borate]nickel(II) 11 3,5-dimetliy1-4-nitro- Bis[dihydrobis(3,5-dimethyl-4-niti-o- Bis[hydrotris(3,5-dimethyl-4-nitro- Bis[tetrakis(3,5-dinietliyl-4-nitropyrazole. pyrazol-1-yl)borate]iron (II) pyrazol-l-yDborate] cobalt (II) pyrazol-l-yl)boratelniekelfll). 12 3-amin0-5-methyl-4nitro- Bis[dil1ydrobis(3-amino-5-methy1-4- Bis[hydrotris(3-amino-5-methyl-4 Bis[tetrakis(3-amin0-5-metliyl-4- pyrazole. nitropyrazol-Lybborate]iron (II) niropyrazol-1-yl) boratejcobaltnlipropyrazol-l-yl) borate1m'ckel- 13 3-amino-4-bromo-5- Bis[dihydrobis(3-amino-4-bromo-5- Bis[hydrotris(3-amino-4-bromo-5- Bis[te trakis(3-amino4-bronio 5- methylpyrazole. methylpyrazol-l-ybborate]iron- 1(IIieIzthylpyraz0l-1-yl)boratelcobaltn efrhfillplyrazol-l-yl)borate] I T 6 14 3-ani1in0-5-phenyl- Bis[dihydrobis(3-ani]jno-5-phenyl Bis[hydrotris(3-anilino-5phenyl- Bis[tetrakis(3-anilino-5-phenylpyraz e. pyrazoLl-yl)borate]iron(II). pyrazol-l-yl)borate]cobalt(II). pyrazol-l-yl)borate]nicke1(II). 15 4-hydroxy-3-methyl-5- Bis[dihydrobis(4-hydroxy-3-methyl- Bis[hydrotris(4-hydroxy-3-methyl- Bis[tetrakis(4-hydroxy-3-methylphenylpyrazole. fi phenylpyrazol-l-yl)borate]iron- 5-pohei(3lI1))yrazol-1-y1)borate} 5- pllzeilylpyrazol-l-yl)borate]- 00 a 1116 e 16 3-methoxy-5-methyl- Bis[dihydrobis(3-methoxy5-methy1- Bis[hydrotris(3 methoxy-5-methyl- Bis[tetrakis(3-meth0xy-5-methylpyrazole. pyrazol-1-yl)borate]iron (II). pyrazol-l-yl) borate] cobalt (II) pyrazol-l-yl) borate]nickel(II) 17 4-hydroxymethylpyrazole. Bisldihydrobis(thydroxymethyl- Bis[l1ydrotris(4-hydroxymetliyl- Bis[tetrakis(A-hydroxymethylpyraz0l-1-y1)borate]iron(1l) pyrazol-l-yl)borate] cobalt (II) pyrazol-l-yl) boratelnickel (II) In another process for preparing the products of this invention, compounds of the formula RB(OH) (column A of Table V) where R is as defined above are treated with PCl to obtain the corresponding compound RBCl This intermediate is then treated with pyrazole and then with aqueous Co(OAc) in the manner of Example XXXII to obtain the cobalt chelate product indicated in column B of Table V.

TABLE V Item mg Compound B. Product from Procedure of Example XXXII 1 C4H\1B(OH)Z Bis(butyltri-l-pyrazolylborate)cobalt(l1). 2 CaHuB(OH)z Bis(cyclohexyltri-l-pyrazolylborate)cobalt 3...--. CpH B(OH) Bis(nonyltrilpyrazolylborate)cobalt(II). 4 C1sH37B(OH) When the salts indicated in column A of Table VI are substituted for CaCl in the metathesis procedure of Example XXI, the metal compounds shown in column B of Table VI are obtained.

TAB LE VI A. Metal salt B. Product from Procedure of Example XXI Other compounds of this invention are prepared by procedures similar to the above. For example, in place of the unsymmetrically substituted lH-pyrazoles in Table I, the corresponding 2H-pyrazoles may be employed to yield the corresponding pyrazol-Z-yl products. In a similar manner, 2H- and 3H-triazoles in place of the lH-triazoles shown in Table II yield the corresponding 1,2,3,- triazol-2-yl and 1,2,3-triazol-3-yl products. Similarly, ZH-tetrazoles in place of the lH-tetrazoles shown in Table III yield the corresponding tetrazol-Z-yl products.

By employing LiGaH, in place of KBH or LiAlH in the examples above, the corresponding gallates are obtained. For example, when LiGaH is employed in place of LiAlH in the procedure of Example XVII, lithium tetra-l-pyrazolyl-gallate is obtained. The use of LiGaH in place of KBH in the procedure of Example X yields bis dihydrodil-pyrazolylgallate nickel (II) Still other compounds of this invention are prepared by employing InCl and TlCl in place of BCl in Examples I, II, and III. For example, when InCl is employed in place of BCl in Example I, there is obtained (tetra-l-pyrazolylindate)iron (III) dichloride. The corresponding thallates are similarly prepared. For example, when TlCl is used in place of BCl in the procedure of Example II, Parts A and B, bis(tetra-1-pyrazolylthallate)iron (II) is obtained.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that this invention is not limited to the specific embodiments thereof except as defined in the appended claims.

The embodiments of the invention in which an ex- ARI.

wherein A is an element of Group III-A of the Periodic Table; R is a member of the class consisting of hydrogen, alkyl containing up to 18 carbon atoms, phenyl and cyano; X is a member of the class consisting of N and CR; Y is a member of the class consisting of N and C-R; R, R and R each represents a member of the class consisting of hydrogen, hydroxy, mercapto, cyano, nitro, nitroso, carboxy, loweralkyl, phenyl, halogen, trifluoromethyl, amino, formyl, loweralkylcarbonyl, benzoyl, loweralkoxy, loweralkoxycarbonyl, loweralkylmercapto, hydroxyloweralkyl, aminoloweralkyl and carboxyloweralkyl with the proviso that any two of R, R and R on adjacent carbon atoms may be taken together to form, with the two carbons to which they are attached, an aryl system on the nitrogen containing ring to which they are attached, said aryl system being a member of the class consisting of a benzo system and a naphtho system; n is an integer from 0-2, inclusive; m is an integer from 1-2, inclusive, equal to the net positive charge on M; and M is a cation selected from the class consisting of hydrogen, ammonium, alkylammonium containing up to 18 carbon atoms, phenylammonium, loweralkylsulfonium and metals having a net positive valence of 1-2, inclusive.

2. A compound as defined by claim 1 wherein A is boron, X is C-R; Y is C-R"; and R, R, R, R and M each represents hydrogen.

3. A compound as defined by claim 1 wherein A is boron, X is C-R; Y is CR"; R represents C C alkyl; and R, R and R each represent loweralky-l; and M represents ammonium.

4. A compound as defined by claim 1 wherein A is boron; X is C Y is C R, R, R and R each represents phenyl; and M represents a metal ion.

5. A compound as defined by claim 1 wherein A is aluminum; X is N; Y is C and R, R, R and M each represents hydrogen.

6. A compound as defined by claim 1 wherein A is aluminum; X is N; Y is CR; R, R and R each represents loweralkyl; and M represents ammonium.

7. A compound as defined by claim 1 wherein A is aluminum; X is N; Y is C-R; R, R and R each represents phenyl; and M represents a metal ion.

8. A compound as defined by claim 1 wherein A is boron; R is lower alkyl; X is C-R; Y is C-R; R, R and R' each represents hydrogen; and M represents a transition metal ion.

9. A compound as defined by claim 1 wherein A is boron; R is hydrogen; X is C- Y is CR'; R, R and R each represents lower alkyl; and M represents a transition metal ion.

10. Bis(tetra-l-pyrazolylborate)M(II) wherein M represents a transition metal.

11. Bis(hydrotri-l-pyrazolylborate)M(II) wherein M represents a transition metal.

12. Bis(dihydrodi-l-pyrazolylborate)M(II) wherein M represents a transition metal.

13. Pyrazolonium tetra-l-pyrazolylborate.

14. Potassium tetra-l-pyrazolylborate monohydrate.

15. A compound as defined by claim 10 wherein M represents iron.

16. A compound as defined by claim 11 wherein M represents cobalt.

17. A compound as defined by claim 12 wherein M represents nickel.

18. A compound as defined by claim 10 wherein M represents copper.

19. Process which comprises heating stepwise a mixture of a compound selected from the class consisting of pyrazoles, triazoles and tetrazoles and a compound of the formula MAR wherein M is a cation selected from the class consisting of hydrogen, ammonium, alkylammonium containing up to 18 carbon atoms, phenylammonium; loweralkylsulfonium and metals having a net positive valence of 1-2, inclusive; A is an element of Group III-A of the Periodic Table; and R is a member of the class consisting of hydrogen, alkyl containing up to 18 carbon atoms, phenyl and cyano.

20. The process as defined by claim 19 wherein said heating steps take place at temperatures in the range 90 C. to 110 C., 180 C. to 220 C., and 260 C. to 290 C.

References Cited by the Applicant E. Buchner and M. Fritsch, Ann., 273, 260 (1893). E. Buchner, Ber. 22, 2166 (1889).

Khim., 33, 3313 (1963).

HENRY R. IILES, Acting Primary Examiner.

15 R. I. GALLAGHER, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Non 3,261,844 July 19, 1966 Swiatoslaw Trofimenko It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

. Column 2, lines 28 to 33, the formula should appear as shown below instead of as in the patent:

l R\ N AR o I Y----- 3 M G) +HR column 4, line 64, for "cobalt [111)" read cobalt (II) column 7, lines 60 and 61, for "copper" read copper(II) column 11, line 71, for "covered" read colored columns 13 and 14, TABLE I, column 3, line' 3 thereof, for "dihydrois" read dihydrobis columns 15 and 16, TABLE I continued, column 2, line 1 thereof, for "4- aminoethylpyrazole" read 4-6- aminoethylpyrazole column 18, line 51, for "R is lower alkyl; X is C-R"; Y is C-R R, R" read R is lower alkyl; X is c-R; Y is (3-12; R R

Signed and sealed this 1st day of August 1967,

(SEAL) Attest:

EDWARD MUFLETCHERJRO EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. A COMPOUND OF THE FORMULA
 19. PROCESS WHICH COMPRISES HEATING STEPWISW A MIXTURE OF A COMPOUND SELECTED FROM THE CLASS CONSISTING OF PYRAZOLES, TRIAZOLES AND TETRAZOLES AND A COMPOUND OF THE FORMULA MAR4 WHEREIN M IS A CATION SELECTED FROM THE CLASS CONSISTING OF HYDROGEN, AMMONIUM, ALKYLAMMONIUM CONTAINING UP TO 18 CARBON ATOMS, PHENYLAMMONIUM, LOWERALKYSULFONIUM AND METALS HAVING A NET POSITIVE VALENCE OF 1-2, INCLUSIVE; A IS AN ELEMENT OF GROUP III-A OF THE PERIODIC TABLE; AND R IS A MEMBER OF THE CLASS CONSISTING OF HYDROGEN, ALKYL CONTAINING UP TO 18 CARBON ATOMS, PHENYL AND CYANO. 